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Kinetic resolution of sulfur-stereogenic sulfoximines by Pd(ii)-MPAA catalyzed C-H arylation and olefination.

ABSTRACT: A direct Pd(ii)-catalyzed kinetic resolution of heteroaryl-enabled sulfoximines through an ortho-C-H alkenylation/arylation of arenes has been developed. The coordination of the sulfoximine pyridyl-motif and the chiral amino acid MPAA ligand to the Pd(ii)-catalyst controls the enantio-discriminating C(aryl)-H activation. This method provides access to a wide range of enantiomerically enriched unreacted aryl-pyridyl-sulfoximine precursors and C(aryl)-H alkenylation/arylation products in good yields with high enantioselectivity (up to >99% ee), and selectivity factor up to >200. The coordination preference of the directing group, ligand effect, geometry constraints, and the transient six-membered concerted-metalation-deprotonation species dictate the stereoselectivity; DFT studies validate this hypothesis.

SUBMITTER: Mukherjee K

PROVIDER: S-EPMC8597855 | biostudies-literature | 2021 Nov

REPOSITORIES: biostudies-literature

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Kinetic resolution of sulfur-stereogenic sulfoximines by Pd(ii)-MPAA catalyzed C-H arylation and olefination.

Mukherjee Kallol K Grimblat Nicolas N Sau Somratan S Ghosh Koushik K Shankar Majji M Gandon Vincent V Sahoo Akhila K AK

Chemical science 20211020 44

A direct Pd(ii)-catalyzed kinetic resolution of heteroaryl-enabled sulfoximines through an <i>ortho</i>-C-H alkenylation/arylation of arenes has been developed. The coordination of the sulfoximine pyridyl-motif and the chiral amino acid MPAA ligand to the Pd(ii)-catalyst controls the <i>enantio</i>-discriminating C(aryl)-H activation. This method provides access to a wide range of enantiomerically enriched unreacted aryl-pyridyl-sulfoximine precursors and C(aryl)-H alkenylation/arylation product ...[more]

PMID: 34820102

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